α-methine substituted thiophene monoazo dye

ABSTRACT

A compound of the formula: ##STR1## wherein K is a radical of a coupling component, R is a radical of a methylene-active compound, X is hydrogen or unsubstituted or substituted alkyl, aryl, or hetaryl and Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl. The present compound is useful for the dyeing of polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers.

The present invention relates to compounds of the general formula I ##STR2## where K is a radical of a coupling component, R is a radical of a methylene-active compound, X is hydrogen or unsubstituted or substituted alkyl, aryl or hetaryl and Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl.

X is hydrogen or, for example, C₁ -C₈ -alkyl which may be further substituted by chlorine, bromine or phenyl, or thienyl, furyl or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or nitro.

Specific examples of alkyl radicals are CH₃, C₂ H₅, C₃ H₇, C₄ H₉, C₅ H₁₁, C₆ H₁₃, C₈ H₁₇ and ##STR3## the abbreviated formula also embracing the n- and iso-radicals.

Specific examples of radicals Y, in addition to those stated above, are CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, C₄ H₉ CO, C₅ H₁₁ CO, C₇ H₁₅ CO, ##STR4## C₆ H₅ CO, CH₃ C₆ H₄ CO, ClC₆ H₄ CO, (CH₃)₂ C₆ H₃ CO, H₃ COC₆ H₄ CO, Cl₂ C₆ H₃ CO, CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO₂, CH₃ C₆ H₄ SO₂, ClC₆ H₄ SO₂, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, ##STR5## COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ H₉, COOC₆ H₅, COOC₆ H₄ CH₃, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₁₃, CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₄ H₉)2, ##STR6##

Methylene-active compounds of the formula H₂ R are, for example, compounds of the formula ##STR7## where Y has the stated meanings, and the compounds of the formulae: ##STR8##

Examples of very important specific compounds of the formula ##STR9##

The coupling components of the formula HK are preferably derived from the aniline, α-naphthylamine, pyrazole, aminopyrazole, indole, thiazole, phenol, naphthol, pyridone or pyridine series, those of the aniline, pyrazole or thiazole series being preferred.

The coupling components HK are, in particular, of the general formulae ##STR10## where R¹ is hydrogen, alkyl, aralkyl or aryl, R² is hydrogen or R³, R³ is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aralkyl or aryl, R² and R³ together with the nitrogen form a saturated heterocyclic structure, R⁴ and R⁵ independently of one another are each hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino or acylamino, R⁶ is cyano, carbamyl, nitro or carbalkoxy and R⁷ is unsubstituted or substituted phenyl, alkyl or aralkyl.

Specific examples of radicals R¹ in addition to those stated above are methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- and p-tolyl and o-, m- and p-chlorophenyl.

Examples of radicals R³ in addition to those stated above are C₁ -C₆ -alkyl which may be substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzyoloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl, and phenyl, benzyl, phenethyl and cyclohexyl.

Specific examples of radicals R³ are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2- -phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl.

R² and R³ together with the nitrogen form, for example, pyrrolidino, piperidino or morpholino.

Examples of suitable radicals R⁴ and R⁵ are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C₁ -C₆ -alkanoylamino, benzylamino, C₁ -C₄ -alkylsulfonylamino and C₁ -C₄ -dialkylaminosulfonylamino.

Examples of radicals R⁶ in addition to those stated above are aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- and sec.-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- and isopropoxyethoxycarbonyl and n-, iso- and sec.-butoxyethoxycarbonyl.

R⁷ is, for example, phenyl which is monosubstituted or polysubstituted by C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, phenoxy, benzyloxy, phenyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -monoalkylamino, C₁ -C₄ -dialkylamino, C₁ -C₄ -alkoxyethoxy, C₁ -C₄ -alkylmercapto, phenylmercapto or C₁ -C₅ -alkanoylamino, such as acetylamino, propionylamino, butyrylamino or valerylamino, or is, for example, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl or benzyl.

The compounds of the formula I have a yellow to blue hue and are particularly useful for dyeing polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers. The dyeings obtained generally possess good or very good fastness properties, particularly on polyesters.

The compounds of the formula I can be prepared by a method in which a 5-formyl compound of the diazo component of the formula ##STR11## is condensed with a compound of the formula

    H.sub.2 R

by a conventional method to give a compound of the formula II ##STR12## this compound is diazotized in a conventional manner, and the product is reacted with a coupling component KH.

However, it is also possible first to diazotize a diazo component of the formula ##STR13## and react the product with a coupling component KH to give a monoazo dye of the formula III ##STR14## and then to condense this dye with a compound of the formula

    H.sub.2 R

to give a methineazo dye of the formula I

The Examples which follow illustrate the preparation. Parts and percentages are by weight, unless stated otherwise.

Of particular importance are compounds of the formula Ia ##STR16## where K¹ is a radical of a coupling component of the aniline or thiazole series, X¹ is hydrogen, C₁ -C₈ -alkyl, benzyl, phenethyl or thienyl, furyl or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, and Y¹ is cyano, a carboxylic ester group or substituted carbamyl.

EXAMPLE 1

(a) 8.3 parts of 2-amino-3-cyano-4-methyl-5-formylthiophene in a mixture of 56.3 parts by volume of glacial acetic acid and 18.7 parts by volume of propionic acid were stirred. 25 parts by volume of 85% strength sulfuric acid were added, after which 16 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were run slowly into the stirred solution at 0°-5° C. and stirring was continued for 4 hours at the same temperature. The diazonium salt solution thus obtained was run slowly into a solution of 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 125 parts of water, 500 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 15 parts of the dye of the formula ##STR17## which dyes polyester fibers in violet hues.

(b) 6.2 parts of the dye described in Example 1a were dissolved in 45 parts by volume of dioxane, 3.8 parts of ethyl cyanoacetate, 1.5 parts of glacial acetic acid and 1.5 parts of piperidine were added and the mixture was stirred for 16 hours at room temperature. Thereafter, 50 parts of water and 50 parts of ice were added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral with water and dried at 40° C. under reduced pressure to give 7 parts of the dye of the formula ##STR18## which dyes polyester fibers in dark blue hues having good lightfastness and fastness to dry heat pleating and setting.

EXAMPLE 2

Using a method similar to that described in Example 1(a), 7.6 parts of 2-amino-3-cyano-5-formylthiophene were reacted with 9.7 parts of N-cyanoethyl-N-ethyl-m-toluidine to give 13 parts of the dye of the formula ##STR19## 3.8 parts of ethyl cyanoacetate, 1.5 parts of glacial acetic acid and 1.5 parts of piperidine were added to 6.0 parts of this dye in 45 parts by volume of dioxane, and the mixture was stirred for 16 hours at room temperature. Thereafter, the dye was precipitated by adding 50 parts of water and 50 parts of ice, the mixture was stirred for 1 hour and the product was filtered off under suction, washed neutral with water and dried to give 7 parts of the dye of the formula ##STR20## which dyes polyesters in fast dark blue hues.

EXAMPLE 3

12.4 parts of the dye of the formula ##STR21## in 80 parts by volume of dioxane were stirred with 6.8 parts of ethyl cyanoacetate, 2.5 parts of glacial acetic acid and 2.5 parts of piperidine for 16 hours at room temperature. Thereafter, the mixture was diluted with 200 parts of an ice/water mixture, and the product was filtered off and dried to give 14.7 parts of the dye of the formula ##STR22## which gives, on polyesters, dark blue dyeings which are lightfast and fast to dry heat pleating and setting.

EXAMPLE 4

Using a method similar to that described in Example 1(b), 13.5 parts of the dye of the formula ##STR23## were reacted with 7.5 parts of n-butyl cyanoacetate to give 14 parts of the dye of the formula ##STR24## Dark blue dyeings having good general fastness properties were obtained on polyesters.

EXAMPLE 5

Using a method similar to that described in Example 1(a), 8.3 parts of 2-amino-3-cyano-4-methyl-5-formylthiophene were reacted with 12.3 parts of N,N-diethyl-3-aminoacetanilide to give 14 parts of the dye of the formula ##STR25## 6.5 parts of this compound were dissolved in 45 parts by volume of dioxane, 3.8 parts of ethyl cyanoacetate, 1.5 parts of glacial acetic acid and 1.5 parts of piperidine were added and the mixture was stirred for 16 hours at room temperature. Working up by a procedure similar to that described in Example 1 gave 7 parts of the dye of the formula ##STR26## which, on polyesters, gives clear blue dyeings which in particular possess very good lightfastness and fastness to dry heat pleating and setting.

The dyes defined in the Table below were obtained similarly to Examples 1-5.

    __________________________________________________________________________      ##STR27##                                                                     Exam-                                                                          ple                                                                            No. X        Y      Y.sup.1                                                                              Y.sup.2    K                     *                   __________________________________________________________________________     6   H        CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                         ##STR28##            dark blue           7   H        CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                         ##STR29##            bluish violet       8   H        CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                         ##STR30##            dark blue           9   H        CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                         ##STR31##            blue                10  H        CN     CN    CN                                                                                         ##STR32##            dark blue           11  H        CN     COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                         ##STR33##            dark blue           12  H        COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                         ##STR34##            bluish violet       13  H        COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                         ##STR35##            dark blue           14  H        COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                         ##STR36##            blue                15  H        COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                         ##STR37##            dark blue           16  H        COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                         ##STR38##            dark blue           17  H        COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           COCH.sub.3                                                                                 ##STR39##            bluish violet       18  H        COOC.sub.2 H.sub.5                                                                    COCH.sub.3                                                                           CN                                                                                         ##STR40##            dark blue           19  H                                                                                        ##STR41##                                                                            CN    COOC.sub.2 H.sub.5                                                                         ##STR42##            dark blue           20  H                                                                                        ##STR43##                                                                            CN    COOC.sub.2 H.sub.5                                                                         ##STR44##            blue                21  H        SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                         ##STR45##            dark blue           22  H        SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                         ##STR46##            dark blue           23  H        SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                         ##STR47##            blue                24  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR48##            bluish violet       25  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR49##            bluish violet       26  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR50##            dark blue           27  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR51##            dark blue           28  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR52##            dark blue           29  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR53##            dark blue           30  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR54##            dark blue           31  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR55##            blue                32  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR56##            blue                33  H        CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR57##            blue                34  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR58##            bluish violet       35  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR59##            bluish violet       36  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR60##            bluish violet       37  CH.sub.3 CN     CN    COOC.sub. 2 H.sub.5                                                                        ##STR61##            dark blue           38  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR62##            dark blue           39  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR63##            dark blue           40  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR64##            dark blue           41  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR65##            dark blue           42  CH.sub.3 CN     CN    COOC.sub.2 H.sub. 5                                                                        ##STR66##            dark blue           43  CH.sub.3 CN     CN    COOC.sub.4 H.sub.9 (n)                                                                     ##STR67##            dark blue           44  CH.sub.3 CN     CN    COOC.sub.4 H.sub.9 (n)                                                                     ##STR68##            blue                45  CH.sub.3 CN     CN    COOC.sub.4 H.sub.9 (n)                                                                     ##STR69##            blue                46  CH.sub.3 CN     CN    COOC.sub.4 H.sub.9 (n)                                                                     ##STR70##            blue                47  CH.sub.3 CN     CN    COOC.sub.4 H.sub.9 (n)                                                                     ##STR71##            dark blue           48  CH.sub.3 CN     CN                                                                                    ##STR72##                                                                                 ##STR73##            dark blue           49  CH.sub.3 CN     CN                                                                                    ##STR74##                                                                                 ##STR75##            dark blue           50  CH.sub.3 CN     CN                                                                                    ##STR76##                                                                                 ##STR77##            dark blue           51  CH.sub.3 CN     CN    CONH.sub.2                                                                                 ##STR78##            dark blue           52  CH.sub.3 CN     COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub. 5                                                                        ##STR79##            navy                53  CH.sub.3 CN     COCH.sub.3                                                                           COOC.sub.2 H.sub.5                                                                         ##STR80##            dark blue           54  CH.sub.3 CN     CN    CONHCH.sub.3                                                                              "                     dark                                                                           blue                55  CH.sub.3 COOC.sub.2 H.sub.5                                                                    CN    CN                                                                                         ##STR81##            blue                56  CH.sub.3 COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.4 H.sub.9                                                                         ##STR82##            dark blue           57  CH.sub.3 COOC.sub.2 H.sub.5                                                                    CN    CON(CH.sub.3).sub.2                                                                        ##STR83##            bluish violet       58  CH.sub.3 CONH.sub.2                                                                            CN    COOC.sub.2 H.sub.5                                                                         ##STR84##            dark blue           59  CH.sub.3 SO.sub.2 CH.sub.3                                                                     CN    COOC.sub.2 H.sub.5                                                                         ##STR85##            dark blue           60  CH.sub.3 CON(CH.sub.3).sub.2                                                                   CN    COOC.sub.2 H.sub.5                                                                         ##STR86##            dark blue           61  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR87##            dark blue           62  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR88##            navy                63  CH.sub.3 CN     CN    COOCH.sub.3                                                                                ##STR89##            navy                64  CH.sub.3 CN     CN    COOCH.sub.3                                                                                ##STR90##            navy                65  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR91##            navy                66  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR92##            violet              67  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR93##            violet              68  CH.sub.3 CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR94##            violet              69  CH.sub.3 CN     CN    CONHCH.sub.3                                                                               ##STR95##            dark blue           70  CH.sub.3 CN     CN    CONHC.sub.2 H.sub.5                                                                        ##STR96##            dark blue           71  CH.sub.3 CN     CN    SO.sub.2 CH.sub.3                                                                          ##STR97##            dark blue           72  CH.sub.3 CN     CN    COCH.sub.3                                                                                 ##STR98##            dark blue           73  CH.sub.3 CN     CN    COOCH.sub.3                                                                                ##STR99##            dark blue           74  CH.sub.3 CN     CN                                                                                    ##STR100##                                                                                ##STR101##           dark blue           75  C.sub.6 H.sub.5                                                                         CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR102##           dark blue           76  C.sub.6 H.sub.5                                                                         CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR103##           dark blue           77  C.sub.6 H.sub.5                                                                         CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR104##           dark blue           78  C.sub.6 H.sub.5                                                                         CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR105##           dark blue           79  C.sub.6 H.sub.5                                                                         CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR106##           dark blue           80  C.sub.6 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                         ##STR107##           dark blue           81  4-CH.sub.3 OC.sub.6 H.sub.4                                                             CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR108##           navy                82  4-CH.sub.3C.sub.6 H.sub.4                                                               CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR109##           navy                83  4-ClC.sub.6 H.sub.4                                                                     CN     CN    COOC.sub.2 H.sub.5                                                                         ##STR110##           navy                __________________________________________________________________________      *Dyeing on polyesters                                                    

EXAMPLE 84

(a) 25 parts of 2-amino-3-cyano-4-methyl-5-formylthiophene were dissolved in 200 parts by volume of ethanol, and 2 parts of glacial acetic acid and 2 parts of piperidine were added. Thereafter, 50 parts by volume of ethyl cyanoacetate were added dropwise at room temperature, and the mixture was stirred for 7 hours at 60° C. and then stirred into 500 parts of an ice/water mixture, and the precipitate was filtered off under suction, washed with water and dried at 60° C. under reduced pressure to give 31.5 parts of 2-amino-3-cyano-4-methyl-5-((β-cyano-β-carboethoxy)-vinyl)-thiophene of the formula ##STR111## which was reacted without further purification.

(b) 13 parts of 2-amino-3-cyano-4-methyl-5-((β-cyano-β-carboethoxy)-vinyl)-thiophene were suspended in 100 parts by volume of 85% strength phosphoric acid, and 16 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added slowly at 0°-5° C. After 2 hours at this temperature, the diazonium salt solution was run into a solution of 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 125 parts of water, 500 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure to give 20 parts of the dye of the formula ##STR112## described in Example 1(b).

EXAMPLE 85

16.2 parts of 2-amino-3-cyano-4-phenyl-5-((β-cyano-β-carboethoxy)-vinyl)-thiophene were suspended in 160 parts by volume of 85% strength phosphoric acid and diazotized with 16 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) at 0°-5° C. After 2 hours at this temperature, the diazonium salt solution was reacted with 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine, using a procedure similar to Example 84(b), to give 23 parts of the dye of the formula ##STR113## which gives, on polyesters, navy dyeings possessing good lightfastness and fastness to dry heat pleating and setting.

EXAMPLE 86

11.6 parts of 2-amino-3-cyano-5-((β-cyano-β-methylaminocarbonyl)-vinyl)-thiophene were suspended in 120 parts by volume of 85% strength phosphoric acid and reacted with 16 parts of nitrosylsulfuric acid at 0°-5° C., and the mixture was stirred for 2 hours at this temperature. The diazonium salt solution was slowly run into a mixture of 7.5 parts of N,N-diethylaniline, 100 parts of water, 300 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the product was washed neutral and dried to give 16 parts of the dye of the formula ##STR114## which, on polyesters, gives dark blue dyeings possessing good general fastness properties.

The compounds defined in the Table below were also obtained similarly to Examples 84-86.

    __________________________________________________________________________      ##STR115##                                                                    Exam-                                                                          ple No.                                                                            X  Y     Y.sup.1                                                                           Y.sup.2                                                                              K                *                                       __________________________________________________________________________     87  H  CN    CN COOCH.sub.3                                                                           ##STR116##      dark blue                               88  H  CN    CN COOCH.sub.3                                                                           ##STR117##      dark blue                               89  H  CN    CN COOCH.sub.3                                                                           ##STR118##      blue                                    90  H  CN    CN COOCH.sub.3                                                                           ##STR119##      blue                                    91  CH.sub.3                                                                          CN    CN COOC.sub.2 H.sub.5                                                                    ##STR120##      dark blue                               92  CH.sub.3                                                                          CN    CN COOC.sub.2 H.sub.5                                                                    ##STR121##      dark blue                               93  CH.sub.3                                                                          CN    CN COOC.sub.2 H.sub.5                                                                    ##STR122##      dark blue                               94  CH.sub.3                                                                          CN    CN COOC.sub.2 H.sub.5                                                                    ##STR123##      dark blue                               95  CH.sub.3                                                                          CN    CN CONHCH.sub.3                                                                          ##STR124##      dark blue                               96  CH.sub.3                                                                          COOCH.sub.3                                                                          CN COOC.sub.2 H.sub.5                                                                    ##STR125##      dark blue                               97  CH.sub.3                                                                          SO.sub.2 CH.sub.3                                                                    CN COOC.sub.2 H.sub.5                                                                    ##STR126##      dark blue                               98  CH.sub.3                                                                          CN    CN COOC.sub.2 H.sub.5                                                                    ##STR127##      bluish violet                           99  C.sub.6 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR128##      dark blue                               100 C.sub.6 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR129##      dark blue                               101 C.sub.6 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR130##      navy                                    __________________________________________________________________________      *Dyeing on polyesters                                                    

The dyes characterized by the substituents in the Table below were prepared similarly to the methods described for Example No. 7.

    __________________________________________________________________________     Example No.                                                                           X  Y  Y.sup.1                                                                           Y.sup.2                                                                              K                 (*)                                    __________________________________________________________________________     102    H  CN CN COOC.sub.2 H.sub.5                                                                    ##STR131##       dark blue                              103    H  CN CN COOC.sub.2 H.sub.5                                                                    ##STR132##       blue                                   104    H  CN CN CN                                                                                    ##STR133##       blue                                   105    H  CN CN COOC.sub.2 H.sub.5                                                                    ##STR134##       blue                                   106    H  CN CN COOC.sub.2 H.sub.5                                                                    ##STR135##       dark blue                              107    H  CN CN COOC.sub.2 H.sub.5                                                                    ##STR136##       blue                                   108    CH.sub.3                                                                          CN CN COOC.sub.2 H.sub.5                                                                    ##STR137##       navy                                   109    CH.sub.3                                                                          CN CN COOC.sub.2 H.sub.5                                                                    ##STR138##       navy                                   110    CH.sub.3                                                                          CN CN CN                                                                                    ##STR139##       blue                                   __________________________________________________________________________      (*) Dyeing on polyesters                                                 

The dyes below were obtained using N,N-dimethylbarbituric acid as the starting material:

    ______________________________________                                          ##STR140##                                                                    Exam-                                                                          ple No.                                                                              X      Y      K                  (*)                                     ______________________________________                                         111   H      CN                                                                                     ##STR141##        dark blue                               112   CH.sub.3                                                                              CN                                                                                     ##STR142##        bluish violet                           113   C.sub.6 H.sub.5                                                                       CN                                                                                     ##STR143##        dark blue                               114   CH.sub.3                                                                              CN                                                                                     ##STR144##        blue                                    115   H      CN                                                                                     ##STR145##        bluish violet                           ______________________________________                                          (*) Dyeing on polyesters                                                  

We claim:
 1. A compound of formula I: ##STR146## wherein X² is cyano and Y² is CN, NO₂, CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, C₄ H₉ CO, C₅ H₁₁ CO, C₇ H₁₅ CO, (C₄ H₉)(C₂ H₅)CHCO, C₆ H₅ CO, CH₃ C₆ H₄ CO, ClC₆ H₄ CO, (CH₃)₂ C₆ H₃ CO, CH₃ OC₆ H₄ CO, Cl₂ C₆ H₂ CO, CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO₂, CH₃ C₆ H₄ SO₂, ClC₆ H₄ SO₂, carboxyl, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, (C₄ H₉)(C₂ H₅)CHCH₂ OOC, CH₃ OC₂ H₄ OOC, C₂ H₅ OC₂ H₄ OOC, C₄ H₉ OC₂ H₄ OOC, C₆ H₅ OOC, CH₃ C₆ H₄ OOC, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₅, CONHC₆ H₁₃, CONH(C₆ H₄ --CH₃ --p), CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₄ H₉)₂, (CH₃)(C₂ H₅)NOC, CONH(C₆ H₄ --OCH₃ --p), CONH(C₆ H₃ --OCH₃ --m, --OCH₃ --p), CONH(C₆ H₄ --Cl--p), C₆ H₅, C₆ H₄ --NO₂ --p, C₆ H₄ --Cl--p, C₆ H₄ --OCH₃ --p, ##STR147## or group ##STR148## is a member selected from the group consisting of ##STR149## X is hydrogen C₁ -C₈ -alkyl, C₁ -C₈ -alkyl substituted by chlorine, bromine or phenyl, thienyl, furyl, phenyl or phenyl substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or nitro; Y is cyano, nitro, CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, C₄ H₉ CO, C₅ H₁₁ CO, C₇ H₁₅ CO, ##STR150## C₆ H₅ CO, CH₃ C₆ H₄ CO, ClC₆ H₄ CO, (CH₃)₂ C₆ H₃ CO, H₃ COC₆ H₄ CO, Cl₂ C₆ H₃ CO, CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO₂, CH₃ C₆ H₄ SO₂, ClC₆ H₄ SO₂, carboxyl, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, COOCH₂ CH(C₄ H₉)(C₂ H₅), COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ H₉, COOC₆ H₅, COOC₆ H₄ CH₃, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₁₃, CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C.sub. 4 H₉)₂, CON(CH₃)(C₂ H₅), ##STR151## and K is derived from HK which is a compound selected from the group consisting of: ##STR152## where R¹ is hydrogen, C₁ -C₈ -alkyl, phenyl, o-, m- or p-tolyl, o-, m- or p-chlorophenyl, benzyl or phenethyl; R² is hydrogen or R³ ; R³ is C₁ -C₆ -alkyl, allyl, methallyl, cyclohexyl, phenethyl, benzyl, phenyl, or C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzyoloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxy-alkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethoxycarbonyl; R² and R³ together with the nitrogen form pyrrolidino, piperidino or morpholino; R⁴ and R⁵ independently of one another are each hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, phenoxy, halogen, C₁ -C₄ -alkylsulfonylamino, C₁ -C₄ -dialkylaminosulfonylamino, C.sub. 1 -C₆ -alkanoylamino; R⁶ is cyano, carbamyl, nitro, methoxycarbonyl, ethoxycarbonyl, n- or isopropoxycarbonyl, n-, iso- or sec-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- or isopropoxyethoxycarbonyl or n-, iso- or sec-butoxyethoxycarbonyl, and R⁷ is phenyl, C₁ -C₄ -alkyl, benzyl or phenyl mono- or polysubstituted by C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, phenoxy, benzoyloxy, phenyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -monoalkylamino, C₁ -C₄ -dialkylamino, C₁ -C₄ -alkoxyethoxy, C₁ -C₄ -alkylmercapto, phenylmercapto or C₁ -C₅ -alkanoylamino.
 2. The compound as claimed in claim 1, of the formula: ##STR153## wherein K' is derived from HK' which is an aniline compound of the formula: ##STR154## or a thiazole compound of the formula: ##STR155## wherein R² is hydrogen or R³, R³ is C₁ -C₆ -alkyl, cyclohexyl, allyl, methallyl, phenethyl, benzyl, phenyl or C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl; R² and R³ together with the nitrogen form pyrrolidino, piperidino or morpholino; R⁴ and R⁵ independently of one another are each hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, phenoxy, halogen, C₁ -C₄ -alkylsulfonylamino, C₁ -C₄ -dialkylaminosulfonylamino, or C₁ -C₆ -alkanoylamino; and R⁷ is phenyl, mono- or polysubstituted by C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, phenoxy, benzoyloxy, phenyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -monoalkylamino, C₁ - C₄ -dialkylamino, C₁ -C₄ -alkoxyethoxy, C₁ -C₄ -alkylmercapto, phenylmercapto or C₁ -C₅ -alkanoylamino, C₁₋₄ alkyl, C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl or benzyl; X is hydrogen, C₁₋₈ -alkyl, benzyl, phenethyl, or thienyl, furyl or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, and Y' is cyano, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, COOCH₂ CH(C₄ H₉ (C₂ H₅), COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ H₉, COOC₆ H₅, COOC₆ H₄ CH₃, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₁₃, CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₄ H₉)₂, CON(CH₃)(C₂ H₅), ##STR156##
 3. The compound as claimed in claim 2, wherein said radical K is derived from a compound selected from the group consisting of ##STR157## wherein R is hydrogen, alkyl, aralkyl or aryl; R² -R⁵ and R⁷ are as defined in claim 2 and R⁶ is cyano, carbamyl, nitro or carbalkoxy.
 4. The compound as claimed in claim 2, wherein said radicals R² and R³ together form a pyrrolidino, piperidino or morpholino.
 5. The compound as claimed in claim 3, wherein said radicals R² and R³ together form a pyrrolidino, piperidino or morpholino.
 6. The compound of claim 2, wherein said R⁴ and R⁵ radicals are selected from the group consisting of hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C₁₋₆ alkanoylamino, benzylamino, C₁₋₄ alkylsulfonylamino and C₁₋₄ dialkylaminosulfonylamino.
 7. The compound of claim 3, wherein said R⁴ and R⁵ radicals are selected from the group consisting of hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C₁₋₆ alkanoylamino, benzylamino, C₁₋₄ alkylsulfonylamino and C₁₋₄ dialkylaminosulfonylamino.
 8. The compound as claimed in claim 3, wherein said R⁶ radical is aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- and sec-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- and isopropoxyethoxycarbonyl or n-, iso- or sec-butoxyethoxycarbonyl.
 9. The compound claimed in claim 2, wherein said substituted alkyl is C₁₋₆ alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl, said aryl radical is phenyl, said aralkyl radical is benzyl or phenethyl and said cycloalkyl radical is cyclohexyl. 